Structured multi-phased personal care composition comprising branched anionic surfactants

ABSTRACT

A multi-phase personal care composition is described that comprises a first visually distinct phase including a structured surfactant component and a second visually distinct phase. The structured surfactant component comprises at least one branched anionic surfactant and from 0 to 10% by weight of the first visually distinct phase, of sodium trideceth sulfate.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional application Ser.No. 60/670,785 filed on Apr. 13, 2005 and U.S. Provisional applicationSer. No. 60/680,114 filed on May 12, 2005 and U.S. Provisionalapplication Ser. No. 60/680,149 filed on May 12, 2005.

FIELD OF THE INVENTION

The present invention relates to a structured multi-phase personal carecomposition that comprises at least one branched anionic surfactant andfrom 0% to 10%, by weight of the first visually distinct phase, ofsodium trideceth sulfate.

BACKGROUND OF THE INVENTION

Personal cleansing compositions that attempt to provideskin-conditioning benefits are known. Desirable personal cleansingcompositions must meet a number of criteria. For example, in order to beacceptable to consumers, a multi-phase personal cleansing compositionmust exhibit good cleaning properties, must exhibit good latheringcharacteristics, must be mild to the skin (not cause drying orirritation) and preferably should even provide a conditioning benefit tothe skin.

Many personal cleansing compositions are aqueous systems comprisingemulsified conditioning oil or other similar materials in combinationwith a lathering surfactant. Although these products provide bothconditioning and cleansing benefits, it is often difficult to formulatea product that deposits sufficient amount of skin conditioning agents onskin during use. In order to combat emulsification of the skinconditioning agents by the cleansing surfactant, large amounts of theskin conditioning agent are added to the compositions. However, thisintroduces another problem associated with these cleansing andconditioning products. Raising the level of skin conditioning agent inorder to achieve increased deposition negatively affects thecompositions speed of lather generation, total lather volume,performance and stability.

Some surfactants used in personal cleansing compositions, such as,sodium trideceth sulfate and similarly homologous chemicals based ontridecanol, also may depress the speed of lather production, althoughsuch compositions provide relatively mild cleansing. It is believed thatthe high level of branching in tridecanol-based surfactants andcompositions that comprise them, exhibits less flash lather as a resultof their water solubility. Moreover, sodium trideceth sulfate andsimilar homologues based on tridecanol, are relatively costly materials,as such, the compositions do not enjoy broad commercial use.

Accordingly, the need still remains for body wash composition thatprovides cleansing with increased lather longevity and improvedlathering characteristics, and skin benefits such as silky skin feel,improved soft skin feel, and improved smooth skin feel. It is desirableto formulate compositions comprising lower levels, or even no sodiumtrideceth sulfate, which have the same beneficial properties as highsodium trideceth sulfate compositions.

SUMMARY OF THE INVENTION

The present invention relates to a multi-phase personal care compositionthat comprises a first visually distinct phase comprising a structuredsurfactant component; and a second visually distinct phase. Thestructured surfactant component comprises at least one branched anionicsurfactant and from 0% to 10%, by weight of the first visually distinctphase, of sodium trideceth sulfate.

The inventors believe that mixtures of branched and linear anionicsurfactants can provide good mildness, structure, and higher flashlather volume than compositions that comprise sodium trideceth sulfate,as the only anionic surfactant. Sufficient mildness can be provided bythe highly branched tridecanol-based anionic surfactant complemented byhigh flash lather volume from linear structured surfactant components.These properties can be accomplished in the same composition by blendingsodium trideceth sulfate with surfactants having a higher proportion oflinear surfactants than sodium trideceth sulfate or by selectingsurfactant which naturally have less branching than sodium tridecethsulfate. A preferred surfactant component comprises a substantial levelof mono-methyl branched surfactants leading to structure and stabilityof structure.

DETAILED DESCRIPTION OF THE INVENTION

The term “ambient conditions” as used herein, refers to surroundingconditions at one (1) atmosphere of pressure, 50% relative humidity, and25° C.

By the term “multi-phase” as used herein, is meant that the phases ofthe present compositions occupy separate but distinct physical spacesinside the package in which they are stored, but are in direct contactwith one another (i.e., they are not separated by a barrier and they arenot emulsified or mixed to any significant degree). In one preferredembodiment of the present invention, the “multi-phase” personal carecompositions comprise at least two visually distinct phases which arepresent within the container as a visually distinct pattern. The patternresults from the combination of the “multi-phase” composition by aprocess herein described. The “patterns” or “patterned” include but arenot limited to the following examples: striped, marbled, rectilinear,interrupted striped, check, mottled, veined, clustered, speckled,geometric, spotted, ribbons, helical, swirl, arrayed, variegated,textured, grooved, ridged, waved, sinusoidal, spiral, twisted, curved,cycle, streaks, striated, contoured, anisotropic, laced, weave or woven,basket weave, spotted, and tessellated. Preferably the pattern isselected from the group consisting of striped, geometric, marbled, andcombinations thereof.

In a preferred embodiment, the striped pattern may be relatively uniformacross the dimension of the package. Alternatively, the striped patternmay be uneven, i.e. wavy, or may be non-uniform in dimension. Thestriped pattern does not need to necessarily extend across the entiredimension of the package. The size of the stripes can be at least about0.1 mm in width and 10 mm in length, preferably at least about 1 mm inwidth and at least 20 mm in length as measured from the packageexterior. The phases may be various different colors, and/or includeparticles, glitter or pearlescent agents in at least one of the phasesin order to offset its appearance from the other phase(s) present.

The term “multi-phase personal care composition” as used herein, refersto compositions intended for topical application to the skin or hair.

The term “visually distinct phase” as used herein, refers to a region ofthe multi-phase personal care composition having one averagecomposition, as distinct from another region having a different averagecomposition, wherein the regions are visible to the unaided naked eye.This would not preclude the distinct regions from comprising two similarphases where one phase could comprise pigments, dyes, particles, andvarious optional ingredients, hence a region of a different averagecomposition. A phase generally occupies a space or spaces havingdimensions larger than the colloidal or sub-colloidal components itcomprises. A phase may also be constituted or re-constituted, collected,or separated into a bulk phase in order to observe its properties, e.g.,by centrifugation, filtration or the like.

The term “stable” as used herein, unless otherwise specified, refers tocompositions that maintain at least two “separate” phases when sittingin undisturbed physical contact at ambient conditions for a period of atleast about 180 days wherein the distribution of the two phases indifferent locations in the package does not significantly change overtime. Compositions of the present invention, preferably exhibit enhancedstability, in that the first visually distinct phase has greater than50% Viscosity Retention measured according to the T-Bar method disclosedherein.

The term “structured surfactant component” as used herein means thetotal of all anionic, nonionic, amphoteric, zwitterionic and cationicsurfactants in a phase. When calculations are based on the structuredsurfactant component, water and electrolyte are excluded from thecalculations involving the structured surfactant component, sincesurfactants as manufactured typically are diluted and neutralized.

The term “structured,” as used herein means having a rheology thatconfers stability on the multi-phase composition. The degree ofstructure is determined by characteristics determined by one or more ofthe following methods the Yield Stress Method, or the Zero ShearViscosity Method or by the Ultracentrifugation Method, all in the TestMethods below. Accordingly, a surfactant phase of the multiphasecomposition of the present invention is considered “structured,” if thesurfactant phase has one or more of the following properties describedbelow according to the Yield Stress Method, or the Zero Shear ViscosityMethod or by the Ultracentrifugation Method. A surfactant phase isconsidered to be structured, if the phase has one or more of thefollowing characteristics:

-   -   A. a Yield Stress of greater than about 0.1 Pascal (Pa), more        preferably greater than about 0.5 Pa, even more preferably        greater than about 1.0 Pa, still more preferably greater than        about 2.0 Pa, still even more preferably greater than about 3        Pa, and even still even more preferably greater than about 5 Pa        as measured by the Yield Stress and Zero Shear Viscosity Method        described hereafter; or    -   B. a Zero Shear Viscosity of at least about 500 Pascal-seconds        (Pa-s), preferably at least about 1,000 Pa-s, more preferably at        least about 1,500 Pa-s, even more preferably at least about        2,000 Pa-s; or    -   C. a Structured Domain Volume Ratio as measured by the        Ultracentrifugation Method described hereafter, of greater than        about 40%, preferably at least about 45%, more preferably at        least about 50%, more preferably at least about 55%, more        preferably at least about 60%, more preferably at least about        65%, more preferably at least about 70%, more preferably at        least about 75%, more preferably at least about 80%, even more        preferably at least about 85%.

Product Form:

The multi-phase personal care composition of the present invention istypically extrudable or dispensable from a package. The multi-phasepersonal care compositions typically exhibit a viscosity of from about1,500 centipoise (cP) to about 1,000,000 cP, as measured by theViscosity Method as described in copending application Ser. No.10/841174 filed on May 7, 2004 titled “Multi-phase Personal CareCompositions.”

When evaluating a structured multi-phase personal care composition, bythe methods described herein, preferably each individual phase isevaluated prior to combining, unless otherwise indicated in theindividual methodology. However, if the phases are combined, each phasecan be separated by centrifugation, ultracentrifugation, pipetting,filtering, washing, dilution, concentration, or combination thereof, andthen the separate components or phases can be evaluated. Preferably, theseparation means is chosen so that the resulting separated componentsbeing evaluated is not destroyed, but is representative of the componentas it exists in the structured multi-phase personal care composition,i.e., its composition and distribution of components therein is notsubstantially altered by the separation means. Generally, multi-phasecompositions comprise domains significantly larger than colloidaldimensions so that separation of the phases into the bulk is relativelyeasy to accomplish while retaining the colloidal or microscopicdistribution of components therein. Preferably, the compositions of thepresent invention are rinse-off formulations, by which is meant theproduct is applied topically to the skin or hair and then subsequently(i.e., within minutes) the skin or hair is rinsed with water, orotherwise wiped off using a substrate or other suitable removal meanswith deposition of a portion of the composition.

In a preferred embodiment of the present invention the structuredmulti-phase personal care composition comprises at least two visuallydistinct phases wherein a first phase is visually distinct from a secondphase. Preferably, the visually distinct phases are packaged in physicalcontact with one another and are stable. Preferably, the visuallydistinct phases form a pattern.

Phases:

The multi-phase personal care compositions of the present inventioncomprise at least two visually distinct phases, wherein the compositioncan have a first phase, a second phase, a third phase, a fourth phase,and so on. The ratio of a first phase to a second phase is typicallyfrom about 1:99 to about 99:1, preferably from 90:10 to about 10:90,more preferably from about 80:20 to about 20:80, even more preferablyabout from 70:30 to about 30:70, still even more preferably about 60:40to about 40:60, even still even more preferably about 50:50.

First Visually Distinct Phase:

The first visually distinct phase of a multi-phase personal carecomposition of the present invention can comprises a structuredsurfactant component. The structured surfactant component comprises atleast of branched anionic surfactant and from 0 to 10% by weight of thefirst visually distinct phase, of sodium trideceth sulfate. Preferably,the structured surfactant component comprises a mixture of surfactants.The structured multi-phased personal care composition comprises fromabout 1% to about 99%, by weight of the composition, of said firstvisually distinct phase.

Structured surfactant component:

The structured surfactant component comprises at least one branchedanionic surfactant. The structured surfactant component preferablycomprises a lathering surfactant or a mixture of lathering surfactants.The structured surfactant component comprises surfactants suitable forapplication to the skin or hair. Suitable surfactants for use hereininclude any known or otherwise effective cleansing surfactant suitablefor application to the skin, and which are otherwise compatible with theother essential ingredients in the structured multi-phase personal carecomposition including water. These surfactants include anionic,nonionic, cationic, zwitterionic, amphoteric surfactants, soap, orcombinations thereof. Preferably, anionic surfactant comprises at least40% of the structured surfactant component, more preferably from about45% to about 95% of the structured surfactant component, even morepreferably from about 50% to about 90%, still more preferably from about55% to about 85%, and even still most preferably at least about 60% ofthe structured surfactant component comprises anionic surfactant.

The multi-phase personal care composition preferably comprises astructured surfactant component at concentrations ranging from about 2%to about 23.5%, more preferably from about 3% to about 21%, even morepreferably from about 4% to about 20.4%, still more preferably fromabout 5% to about 20%, still even more preferably from about 13% toabout 18.5%, and even still even more preferably from about 14% to about18%, by weight of the first visually distinct phase.

The first visually distinct phase comprising the structured surfactantcomponent is preferably a structured domain comprising surfactants. Thestructured domain enables the incorporation of high levels of benefitcomponents in a separate phase that are not emulsified in thecomposition. In a preferred embodiment the structured domain is anopaque structured domain. The opaque structured domain is preferably alamellar phase. The lamellar phase produces a lamellar gel network. Thelamellar phase can provide resistance to shear, adequate yield tosuspend particles and droplets and at the same time provides long termstability, since it is thermodynamically stable. The lamellar phasetends to have a higher viscosity thus minimizing the need for viscositymodifiers.

The first visually distinct phase typically provides a Total LatherVolume of at least about 600 ml, preferably greater than about 800 ml,more preferably greater than about 1000 ml, even more preferably greaterthan about 1200 ml, and still more preferably greater than about 1500ml, as measured by the Lather Volume Test described hereafter. The firstvisually distinct phase preferably has a Flash Lather Volume of at leastabout 300 ml, preferably greater than about 400 ml, even more preferablygreater than about 500 ml, as measured by the Lather Volume Testdescribed hereafter.

Suitable surfactants are described in McCutcheon's, Detergents andEmulsifiers, North American edition (1986), published by alluredPublishing Corporation; and McCutcheon's, Functional Materials, NorthAmerican Edition (1992); and in U.S. Pat. No. 3,929,678 issued toLaughlin, et al on Dec. 30, 1975.

Preferred linear anionic surfactants for use in the structuredsurfactant phase of the multiphase, personal care composition includeammonium lauryl sulfate, ammonium laureth sulfate, sodium laurylsulfate, sodium laureth sulfate, potassium laureth sulfate, sodiumlauryl sarcosinate, sodium lauroyl sarcosinate, lauryl sarcosine, cocoylsarcosine, ammonium cocoyl sulfate, potassium lauryl sulfate, andcombinations thereof.

Amphoteric surfactants are suitable for use in the multiphasecomposition of the present invention. The amphoteric surfactants includethose that are broadly described as derivatives of aliphatic secondaryand tertiary amines in which the aliphatic radical can be straight orbranched chain and wherein one of the aliphatic substituents containsfrom about 8 to about 18 carbon atoms and one contains an anionic watersolubilizing group, e.g., carboxy, sulfonate, sulfate, phosphate, orphosphonate. Examples of compounds falling within this definition aresodium 3-dodecyl-aminopropionate, sodium 3-dodecylaminopropanesulfonate, sodium lauryl sarcosinate, and N-alkyltaurines. Zwitterionicsurfactants suitable for use include those that are broadly described asderivatives of aliphatic quaternary ammonium, phosphonium, and sulfoniumcompounds, in which the aliphatic radicals can be straight or branchedchain, and wherein one of the aliphatic substituents contains from about8 to about 18 carbon atoms and one contains an anionic group, e.g.,carboxy, sulfonate, sulfate, phosphate, or phosphonate. Zwitterionicsurfactants suitable for use in the multiphase, personal carecomposition include betaines, including cocoamidopropyl betaine.

Non-limiting examples of preferred nonionic surfactants for use hereinare those selected form the group consisting of glucose amides, alkylpolyglucosides, sucrose cocoate, sucrose laurate, alkanolamides,ethoxylated alcohols and mixtures thereof. In a preferred embodiment thenonionic surfactant is selected from the group consisting of glycerylmonohydroxystearate, isosteareth-2, trideceth-3, hydroxystearic acid,propylene glycol stearate, PEG-2 stearate, sorbitan monostearate,glyceryl laurate, laureth-2, cocamide monoethanolamine, lauramidemonoethanolamine, and mixtures thereof.

Mixtures of anionic surfactants can be used in some embodiments,including mixtures of linear and branched surfactants, and anionicsurfactants combined with nonionic, amphoteric, and/or zwitterionicsurfactants.

An electrolyte, if used, can be added per se to the multiphase personalcare composition or it can be formed in situ via the counterionsincluded in one of the raw materials. The electrolyte preferablyincludes an anion comprising phosphate, chloride, sulfate or citrate anda cation comprising sodium, ammonium, potassium, magnesium or mixturesthereof. Some preferred electrolytes are sodium chloride, ammoniumchloride, sodium or ammonium sulfate. The electrolyte is preferablyadded to the structured surfactant phase of the composition in theamount of from about 0.1% to about 15% by weight, preferably from about1% to about 6% by weight, more preferably from about 3% to about 6%, byweight of the structured surfactant composition.

In one embodiment of the present invention, the multiphase, personalcare composition comprises a structured surfactant phase comprising amixture of at least one nonionic surfactant, and an electrolyte. Inanother embodiment, the surfactant phase can comprise a mixture ofsurfactants, water, at least one anionic surfactant, an electrolyte, andat least one alkanolamide.

Branched Anionic Surfactants:

At least one anionic surfactant comprising anionic surfactant moleculesof the present invention is preferably branched. A surfactant moleculeis branched when the hydrocarbon tail of the surfactant moleculecomprises at least one ternary or quaternary carbon atom, such that amethyl, ethyl, propyl, butyl, pentyl or hexyl side chain extends fromthe hydrocarbon backbone. The hydrocarbon backbone is described by thelongest hydrocarbon length in the hydrocarbon tail. A side chain in thebranched hydrocarbon of a surfactant molecule can be described by itsposition on the backbone, counting from the first carbon attached to ahydrophilic atom, enumerated as carbon number 1, the adjacent carbon onthe backbone being carbon number 2, and so on. Side chains are alsodescribed by their length, a single carbon side chain denoted methyl; a2-carbon length denoted ethyl, and so on. Side chains that have theirown branching are denoted by conventional nomenclature techniques, e.g.,isopropyl, but are less common. Anionic surfactant molecules which donot have branching are linear anionic surfactant molecules, andsurfactants comprising a preponderance of linear anioinic surfactantmolecules as indicated hereafter are linear anionic surfactants. Mostanionic surfactants derived from common natural sources such as coconutand palm, are linear anionic surfactants, such as ammonium laurylsulfate, sodium lauryl ether sulfate. Linear anionic surfactants canalso be derived from other sources including synthetic.

Because an anionic surfactant typically comprises a mixture of differenttypes of surfactant molecules, anionic surfactants can be called linearor branched depending on the relative amounts of individual surfactantmolecules of different types that comprise the anionic surfactant. Forexample, sodium tridecyl sulfate and sodium trideceth sulfate can becalled branched surfactants because they typically comprise nearly all(>95%) branched surfactant molecules. For the purposes of the presentinvention, an anionic surfactant is considered branched surfactant whenat least 10% of its hydrocarbon chains are branched molecules.

Branched anionic surfactants comprise surfactant molecules havingdifferent kinds of branching. Some branched anionic surfactants, such astridecanol based sulfates such as sodium trideceth sulfate, comprise ahigh level of branching, with over 80% of surfactant moleculescomprising at least 2 branches and having an average of about 2.7branches per molecule in some sodium trideceth sulfates. Other branchedanionic surfactants, such as C₁₂₋₁₃ alkyl sulfate derived from Safol ™23 alcohol (Sasol, Inc, Houston, Tex., USA) comprise a mixture of about50-55% linear anionic surfactant molecules, with about 15-30% branchedsurfactant molecules. For the purposes of the present invention, anionicsurfactants comprising more than 10% branched surfactant molecules, buthaving an average of less than 2.0 branches per molecule, are consideredmonomethyl branched anionic surfactants.

Branching information for many surfactants is typically known orobtainable from suppliers of branched alcohol feedstocks. For example,Sasol publishes the following information related to Safol ™ 23 primaryalcohol: Linear Alcohol Isomers  50% Mono-Methyl Alcohol Isomers  30%Other Primary Alcohol Isomers <20% Total 100%Safol ™ 23 alcohol can be sulfated, for example in an SO₃/air streamfalling film reactor followed by rapid neutralization with sodiumhydroxide to produce sodium C₁₂₋₁₃ alkyl sulfate, a process known in theart. Since the sulfation process involves no rearrangement of thehydrocarbon backbone, the backbone of the C₁₂₋₁₃ alkyl sulfate has thesame structure as the Safol ™ 23 alcohol, and is a branched anionicsurfactant, and is also a monomethyl branched anionic surfactant. Othersuppliers of alcohols provide similar information on their primaryalcohols, e.g., Shell Chemical for the Neodol ™ primary alcohols. In theabsence of published analytical information by established methods frommaterial suppliers on branching of a surfactant or its feedstockalcohol, analytical techniques known to those skilled in the art can beused to determine branching. For example, when the structure of thehydrocarbon tail is not very complex (i.e., less than about a dozenmajor components), a gas chromatography-mass spectrometry (GC-MS)technique can be used, involving oxidation of the alcohol in acetone(cosolvent) by a 3.3 M H₂CRO₄ Jones Reagent to a fatty acid followed byoxazoline derivatization using 2-amino, 2-methyl, 1-propanol at 200 Cfor 2 hours, dilution with CHCl₃ and subsequent washing with distilledwater, drying with sodium sulfate prior to injection into a splitinjection (280 C) or on-column injection. A typical GC program is 80-320C at 5 C/min rate on a 30 m×0.25 mm DB-1 (0.25 uM film) column, and cangive specific information on branching location for a majority of ahydrocarbon tail of an anionic surfactant. When co-elution of speciesand/or elution of unknown components occur, GC-MS is able to obtain theamount of branched components, which is taken as 100% minus the sum ofn-C12 and n-C13 eluted. Typically, n-C₁₁, n-C₁₂ and n-C₁₃ elution timesare known for a column and/or can be obtained by simple running ofstandards which are available. By convention for our invention,inventors sum all oxazoline peaks in the GC window between n-C₁₁ andn-C₁₂, said peaks are the branched C₁₂ peaks; sum all oxazoline peaks inthe GC window between n-C₁₂ and n-C₁₃, said peaks are the branched C₁₃peaks; dividing the peak areas obtained by the total area obtained,including linear C₁₂ and linear C₁₃, to obtain the fractional amount ofeach component. By our convention, the sum of the peak fractions in thebranched C₁₂ and branched C₁₃ windows, added together, is the fractionof branched molecules, which can be expressed as a percentage. Theintegrated area under each GC peak is the peak information used in thecalculations. If necessary, the surfactant can even be obtained byextraction from a composition first, e.g. by filtration such as crossflow filtration. From the GC data, the number of branch points perhydrocarbon chain is summed, multiplying number of branches per moleculeby mole fraction for each species identified to obtain an average degreeof branching per molecule for the surfactant. For example, 50% ofmolecules having 1 branch point with 50% linear molecules is an averagedegree of branching of 0.5. For highly branched molecules (>1.25 averagedegree of branching), such as sodium trideceth sulfate, determiningdegree of branching from the GC spectra can be difficult and requirespecialized equipment, so instead is determined from conventional NMRtechniques, using the ratio of ternary to secondary carbon-carbon bondsin the hydrocarbon tail to determine average degree of branching.

Branched anionic surfactants include but are not limited to thefollowing surfactants: sodium trideceth sulfate, sodium tridecylsulfate, sodium C₁₂₋₁₃ alkyl sulfate, sodium C₁₂₋₁₅ alkyl sulfate,sodium C₁₁₋₁₅ alkyl sulfate, sodium C₁₂₋₁₈ alkyl sulfate, sodium C₁₀₋₁₆alkyl sulfate, sodium C₁₂₋₁₃ pareth sulfate, sodium C₁₂₋₁₃ pareth-nsulfate, and sodium C₁₂₋₁₄ pareth-n sulfate. Other salts of all theaforementioned surfactants are useful, such as TEA, DEA, ammonia,potassium salts. Useful alkoxylates include the ethylene oxide,propylene oxide and EO/PO mixed alkoxylates. Phosphates, carboxylatesand sulfonates prepared from branched alcohols are also useful anionicbranched surfactants. Branched surfactants can be derived from syntheticalcohols such as the primary alcohols from the liquid hydrocarbonsproduced by Fischer-Tropsch condensed syngas, for example Safol ™ 23Alcohol available from Sasol North America, Houston, Tex.; fromsynthetic alcohols such as Neodol ™ 23 Alcohol available from ShellChemicals, USA; from synthetically made alcohols such as those describedin U.S. Pat. No. 6,335,312 issued to Coffindaffer, et al on Jan. 1,2002. Preferred alcohols are Safol ™ 23 and Neodol ™ 23. Preferredalkoxylated alcohols are Safol ™ 23-3 and Neodol ™ 23-3. Sulfates can beprepared by conventional processes to high purity from a sulfur basedSO₃ air stream process, chlorosulfonic acid process, sulfuric acidprocess, or Oleum process. Preparation via SO₃ air stream in a fallingfilm reactor is a preferred sulfation process.

Monomethyl branched anionic surfactants include but are not limited tothe branched anionic sulfates derived from Safol ™ 23-n and Neodol ™23-n as previously described, where n is an integer between 1 and about20. Fractional alkloxylation is also useful, for example bystoichiometrically adding only about 0.3 moles EO, or 1.5 moles EO, or2.2 moles EO, based on the moles of alcohol present, since the molecularcombinations that result are in fact always distributions of alkoxylatesso that representation of n as an integer is merely an averagerepresentation. Preferred monomethyl branched anionic surfactantsinclude a C₁₂₋₁₃ alkyl sulfate derived from the sulfation of Safol ™ 23,which has about 28% branched anionic surfactant molecules; and a C12-13pareth sulfate derived from Neodol ™ 23-3, which has about 10-18%branched anionic surfactant molecules.

When the anionic surfactant is a branched anionic primary sulfate, itmay contain some of the following branched anionic surfactant molecules:4-methyl undecyl sulfate, 5-methyl undecyl sulfate, 7-methyl undecylsulfate, 8-methyl undecyl sulfate, 7-methyl dodecyl sulfate,8-methyl-dodecyl sulfate, 9-methyl dodecyl sulfate, 4,5-dimethyl decylsulfate, 6,9-dimethyl decyl sulfate, 6,9-dimethyl undecyl sulfate,5-methyl-8-ethyl undecyl sulfate, 9-methyl undecyl sulfate,5,6,8-trimethyl decyl sulfate, 2-methyl dodecyl sulfate, and 2-methylundecyl sulfate,. When the anionic surfactant is a primary alkoxylatedsulfate, these same molecules may be present as the n=0 unreactedalcohol sulfates, in addition to the typical alkoxylated adducts thatresult from alkoxylation (e.g., Neodol ™ 23-3 mol EO retains typically16% unreacted Neodol ™ 23 with 57% of molecules having 1 to 5 EOmolecules reacted, according to Shell Chemicals technical literature,‘Typical Distributions of NEODOL Ethoxylate Adducts”).

Second Visually Distinct Phase:

The second visually distinct phase is distinguishable from the firstvisually distinct phase by having a different color, opacity maycomprise a structured surfactant or a non-lathering structured AqueousPhase.

The second visually distinct phase may comprise a structured surfactantidentical to the structured surfactant in the first visually distinctphase; described in detail above.

The second visually distinct phase of the multi-phase personal carecompositions of the present invention can comprise a structured aqueousphase that comprises a water structurant and water. The structuredaqueous phase can be hydrophilic and in a preferred embodiment thestructured aqueous phase is a hydrophilic, non-lathering gelled waterphase. In addition, the structured aqueous phase typically comprisesless than about 5%, preferably less than about 3%, and more preferablyless than about 1%, by weight of the structured aqueous phase, of asurfactant. In one embodiment of the present invention, the structuredaqueous phase is free of lathering surfactant in the formulation. Apreferred structured aqueous phase is a non-lathering structured aqueousphase as described in published U.S. Patent Application No.2005/0143269A1 entitled “Multi-phase Personal Cleansing CompositionsContaining A Lathering Cleansing Phase And A Non-Lathering StructuredAqueous Phase.”

The structured aqueous phase of the present invention can comprise fromabout 30% to about 99%, by weight of the structured aqueous phase, ofwater. The structured aqueous phase generally comprises more than about50%, preferably more than about 60%, even more preferably more thanabout 70%, and still more preferably more than about 80%, by weight ofthe structured aqueous phase, of water.

The structured aqueous phase will typically have a pH of from about 5 toabout 9.5, more preferably about 7. A water structurant for thestructured aqueous phase can have a net cationic charge, net anioniccharge, or neutral charge. The structured aqueous phase of the presentcompositions can further comprise optional ingredients such as,pigments, pH regulators (e.g. triethanolamine), and preservatives.

The structured aqueous phase can comprise from about 0.1% to about 30%,preferably from about 0.5% to about 20%, more preferably from about 0.5%to about 10%, and even more preferably from about 0.5% to about 5%, byweight of the structured aqueous phase, of a water structurant.

The water structurant is typically selected from the group consisting ofinorganic water structurants, charged polymeric water structurants,water soluble polymeric structurants, associative water structurants,and mixtures thereof. Non-limiting examples of inorganic waterstructurants include silicas, polymeric gellants such as polyacrylates,polyacrylamides, starches, modified starches, crosslinked polymericgellants, copolymers, and mixtures thereof. Non-limiting examples ofcharged polymeric water structurants for use in the multi-phase personalcare composition include Acrylates/Vinyl Isodecanoate Crosspolymer(Stabylen 30 from 3V), Acrylates/C10-30 Alkyl Acrylate Crosspolymer(Pemulen TR1 and TR2), Carbomers, Ammonium Acryloyldimethyltaurate/VPCopolymer (Aristoflex AVC from Clariant), AmmoniumAcryloyldimethyltaurate/Beheneth-25 Methacrylate Crosspolymer(Aristoflex HMB from Clariant), Acrylates/Ceteth-20 Itaconate Copolymer(Structure 3001 from National Starch), Polyacrylamide (Sepigel 305 fromSEPPIC), and mixtures thereof. Non-limiting examples of water solublepolymeric structurants for use in the multi-phase personal carecomposition include cellulose gums and gel, and starches. Non-limitingexamples of associative water structurants for use in the multi-phasepersonal care composition include xanthum gum, gellum gum, pectins,alginates such as propylene glycol alginate, and mixtures thereof.

Additional Ingredients:

The phases of the multi-phase personal care composition, preferably thefirst visually distinct phase, can further comprise a polymeric phasestructurant. The compositions of the present invention typically cancomprise from about 0.05% to about 10%, preferably from about 0.1% toabout 4%, of a polymeric phase structurant. Non-limiting examples ofpolymeric phase structurant include but are not limited to the followingexamples: naturally derived polymers, synthetic polymers, crosslinkedpolymers, block copolymers, copolymers, hydrophilic polymers, nonionicpolymers, anionic polymers, hydrophobic polymers, hydrophobicallymodified polymers, associative polymers, and oligomers.

Preferably the polymeric phase structurant can be crosslinked andfurther comprise a crosslinking. These polymeric phase structurantuseful in the present invention are more fully described in U.S. Pat.No. 5,087,445, to Haffey et al., issued Feb. 11, 1992; U.S. Pat. No.4,509,949, to Huang et al., issued Apr. 5, 1985, U.S. Pat. No.2,798,053, to Brown, issued Jul. 2, 1957. See also, CTFA InternationalCosmetic Ingredient Dictionary, fourth edition, 1991, pp. 12 and 80.

The phase of the present compositions, preferably the first visuallydistinct phase, optionally can further comprise a liquid crystallinephase inducing structurant, which when present is at concentrationsranging from about 0.3% to about 15%, by weight of the phase, morepreferably at from about 0.5% to about 5% by weight of the phase.Suitable liquid crystalline phase inducing structurants include fattyacids (e.g. lauric acid, oleic acid, isostearic acid, linoleic acid)ester derivatives of fatty acids (e.g. propylene glycol isostearate,propylene glycol oleate, glyceryl isostearate) fatty alcohols,trihydroxystearin (available from Rheox, Inc. under the trade nameTHIXCIN™ R). Preferably, the liquid crystalline phase inducingstructurant is selected from lauric acid, trihydroxystearin, laurylpyrrolidone, and tridecanol.

The structured multi-phase personal care compositions of the presentinvention can additionally comprise an organic cationic depositionpolymer in the one or more phases as a deposition aid for the benefitagents described herein. Suitable cationic deposition polymers for usein the structured multi-phase personal care compositions of the presentinvention contain cationic nitrogen-containing moieties such asquaternary ammonium or cationic protonated amino moieties. The cationicprotonated amines can be primary, secondary, or tertiary amines(preferably secondary or tertiary), depending upon the particularspecies and the selected pH of the structured multi-phase personal carecomposition. Suitable cationic deposition polymers that would be usefulin the compositions of the present invention are disclosed in theco-pending and commonly assigned U.S. Patent Application No. 60/628,036filed on Nov. 15, 2003 by Wagner, et al titled “Depositable Solids.”

One or more of the phases of the multiphase personal care compositioncan comprise a variety of additional optional ingredients such as shinyparticles, beads, exfoliating beads. Such optional ingredients are mosttypically those materials approved for use in cosmetics and that aredescribed in reference books such as the CTFA Cosmetic IngredientHandbook, Second Edition, The Cosmetic, Toiletries, and FragranceAssociation, Inc. 1988, 1992.

Other non limiting examples of these optional ingredients includevitamins and derivatives thereof (e.g., ascorbic acid, vitamin E,tocopheryl acetate, and the like), sunscreens; thickening agents,preservatives for maintaining the anti microbial integrity of thecleansing compositions, anti-acne medicaments, antioxidants, skinsoothing and healing agents such as aloe vera extract, allantoin and thelike, chelators and sequestrants, skin lightening agents, and agentssuitable for aesthetic purposes such as fragrances, essential oils, skinsensates, pigments, pearlescent agents and essential oils and fragrance.

The preferred pH range of the structured multi-phase personal carecomposition is from about 5 to about 8.

Test Methods:

Yield Stress and Zero Shear Viscosity Method:

The Yield Stress and Zero Shear Viscosity of a phase of the presentcomposition, can be measured either prior to combining in thecomposition, or after combining in the composition by separating thephase by suitable physical separation means, such as centrifugation,pipetting, cutting away mechanically, rinsing, filtering, or otherseparation means.

A controlled stress rheometer such as a TA Instruments AR2000 Rheometeris used to determine the Yield Stress and Zero Shear Viscosity. Thedetermination is performed at 25° C. with the 4 cm diameter parallelplate measuring system and a 1 mm gap. The geometry has a shear stressfactor of 79580 m⁻³ to convert torque obtained to stress.

First a sample of the phase is obtained and placed in position on therheometer base plate, the measurement geometry (upper plate) moving intoposition 1 mm above the base plate. Excess phase at the geometry edge isremoved by scraping after locking the geometry. If the phase comprisesparticles discernible to the eye or by feel (beads, e.g.) which arelarger than about 150 microns in number average diameter, the gapsetting between the base plate and upper plate is increased to thesmaller of 4 mm or 8-fold the diameter of the 95^(th) volume percentileparticle diameter. If a phase has any particle larger than 5 mm in anydimension, the particles are removed prior to the measurement.

The determination is performed via the programmed application of acontinuous shear stress ramp from 0.1 Pa to 1,000 Pa over a timeinterval of 5 minutes using a logarithmic progression, i.e., measurementpoints evenly spaced on a logarithmic scale. Thirty (30) measurementpoints per decade of stress increase are obtained. Stress, strain andviscosity are recorded. If the measurement result is incomplete, forexample if material flows from the gap, results obtained are evaluatedand incomplete data points excluded. The Yield Stress is determined asfollows. Stress (Pa) and strain (unitless) data are transformed bytaking their logarithms (base 10). Log(stress) is graphed vs.log(strain) for only the data obtained between a stress of 0.2 Pa and2.0 Pa, about 30 points. If the viscosity at a stress of 1 Pa is lessthan 500 Pa-sec but greater than 75 Pa-sec, then log(stress) is graphedvs. log(strain) for only the data between 0.2 Pa and 1.0 Pa, and thefollowing mathematical procedure is followed. If the viscosity at astress of 1 Pa is less than 75 Pa-sec, the zero shear viscosity is themedian of the 4 highest viscosity values (i.e., individual points)obtained in the test, the yield stress is zero, and the followingmathematical procedure is not used. The mathematical procedure is asfollows. A straight line least squares regression is performed oh theresults using the logarithmically transformed data in the indicatedstress region, an equation being obtained of the form:(1) Log(strain)=m*Log(stress)+b

Using the regression obtained, for each stress value (i.e., individualpoint) in the determination between 0.1 and 1,000 Pa, a predicted valueof log(strain) is obtained using the coefficients m and b obtained, andthe actual stress, using Equation (1). From the predicted log(strain), apredicted strain at each stress is obtained by taking the antilog (i.e.,10^(x) for each x). The predicted strain is compared to the actualstrain at each measurement point to obtain a % variation at each point,using Equation (2).(2) % variation=100*(measured strain−predicted strain)/measured strain

The Yield Stress is the first stress (Pa) at which % variation exceeds10% and subsequent (higher) stresses result in even greater variationthan 10% due to the onset of flow or deformation of the structure. TheZero Shear Viscosity is obtained by taking a first median value ofviscosity in Pascal-seconds (Pa-sec) for viscosity data obtained betweenand including 0.1 Pa and the Yield Stress. After taking the first medianviscosity, all viscosity values greater than 5-fold the first medianvalue and less than 0.2×the median value are excluded, and a secondmedian viscosity value is obtained of the same viscosity data, excludingthe indicated data points. The second median viscosity so obtained isthe Zero Shear Viscosity.

Lather Volume Test:

Lather volume of a first visually distinct phase, a structuredsurfactant component or a structured domain of a structured multi-phasepersonal care composition, is measured using a graduated cylinder and arotating apparatus. A 1,000 ml graduated cylinder is used which ismarked in 10 ml increments and has a height of 14.5 inches at the 1,000ml mark from the inside of its base (for example, Pyrex No. 2982).Distilled water (100 grams at 25° C.) is added to the graduatedcylinder. The cylinder is clamped in a rotating device, which clamps thecylinder with an axis of rotation that transects the center of thegraduated cylinder. Inject 0.50 grams of a structured surfactantcomponent or first visually distinct phase from a syringe (weigh toensure proper dosing) into the graduated cylinder onto the side of thecylinder, above the water line, and cap the cylinder. When the sample isevaluated, use only 0.25 cc, keeping everything else the same. Thecylinder is rotated for 20 complete revolutions at a rate of about 10revolutions per 18 seconds, and stopped in a vertical position tocomplete the first rotation sequence. A timer is set to allow 15 secondsfor lather generated to drain. After 15 seconds of such drainage, thefirst lather volume is measured to the nearest 10 ml mark by recordingthe lather height in ml up from the base (including any water that hasdrained to the bottom on top of which the lather is floating).

If the top surface of the lather is uneven, the lowest height at whichit is possible to see halfway across the graduated cylinder is the firstlather volume (ml). If the lather is so coarse that a single or only afew foam cells which comprise the lather (“bubbles”) reach across theentire cylinder, the height at which at least 10 foam cells are requiredto fill the space is the first lather volume, also in ml up from thebase. Foam cells larger than one inch in any dimension, no matter wherethey occur, are designated as unfilled air instead of lather. Foam thatcollects on the top of the graduated cylinder but does not drain is alsoincorporated in the measurement if the foam on the top is in its owncontinuous layer, by adding the ml of foam collected there using a rulerto measure thickness of the layer, to the ml of foam measured up fromthe base. The maximum lather height is 1,000 ml (even if the totallather height exceeds the 1,000 ml mark on the graduated cylinder). 30seconds after the first rotation is completed, a second rotationsequence is commenced which is identical in speed and duration to thefirst rotation sequence. The second lather volume is recorded in thesame manner as the first, after the same 15 seconds of drainage time. Athird sequence is completed and the third lather volume is measured inthe same manner, with the same pause between each for drainage andtaking the measurement.

The lather results after each sequence are added together and the TotalLather Volume determined as the sum of the three measurements, inmilliters (“ml”). The Flash Lather Volume is the result after the firstrotation sequence only, in ml, i.e., the first lather volume.Compositions according to the present invention perform significantlybetter in this test than similar compositions in conventional emulsionform.

Ultracentrifugation Method:

The Ultracentrifugation Method is used to determine the percent of astructured domain or an opaque structured domain that is present in astructured multi-phase personal care composition that comprises a firstvisually distinct phase comprising a structured surfactant component.The method involves the separation of the composition byultracentrifugation into separate but distinguishable layers. Thestructured multi-phase personal care composition of the presentinvention can have multiple distinguishable layers, for example anon-structured surfactant layer, a structured surfactant layer, and abenefit layer.

First, dispense about 4 grams of multi-phase personal care compositioninto Beckman Centrifuge Tube (11×60 mm). Next, place the centrifugetubes in an Ultracentrifuge (Beckman Model L8-M or equivalent) andultracentrifuge using the following conditions: 50,000 rpm, 18 hours,and 25° C.

After ultracentrifuging for 18 hours, determine the relative phasevolume by measuring the height of each layer visually using anElectronic Digital Caliper (within 0.01 mm). First, the total height ismeasured as H_(a) which includes all materials in the ultracentrifugetube. Second, the height of the benefit layer is measured as H_(b).Third, the structured surfactant layer is measured as H_(c). The benefitlayer is determined by its low moisture content (less than 10% water asmeasured by Karl Fischer Titration). It generally presents at the top ofthe centrifuge tube. The total surfactant layer height (H_(s)) can becalculated by this equation:H _(s) =H _(a) −H _(b)

The structured surfactant layer components may comprise several layersor a single layer. Upon ultracentrifugation, there is generally anisotropic layer at the bottom or next to the bottom of theultracentrifuge tube. This clear isotropic layer typically representsthe non-structured micellar surfactant layer. The layers above theisotropic phase generally comprise higher surfactant concentration withhigher ordered structures (such as liquid crystals). These structuredlayers are sometimes opaque to naked eyes, or translucent, or clear.There is generally a distinct phase boundary between the structuredlayer and the non-structured isotropic layer. The physical nature of thestructured surfactant layers can be determined through microscopy underpolarized light. The structured surfactant layers typically exhibitdistinctive texture under polarized light. Another method forcharacterizing the structured surfactant layer is to use X-raydiffraction technique. Structured surfactant layer display multiplelines that are often associated primarily with the long spacings of theliquid crystal structure. There may be several structured layerspresent, so that H_(c) is the sum of the individual structured layers.If a coacervate phase or any type of polymer-surfactant phase ispresent, it is considered a structured phase.

Finally, the structured domain volume ratio is calculated as follows:Structured Domain Volume Ratio=H _(c) /H _(s)*100%

If there is no benefit phase present, use the total height as thesurfactant layer height, H_(s)=H_(a).

T- Bar Method for Assessing Structured Surfactant Stability In Presenceof Lipid

The stability of a surfactant-containing phase (“cleansing phase” or“first visually distinct phase”) in the presence of lipid can beassessed using a T-Bar Viscosity Method. The apparatus for T-Barmeasurement includes a Brookfield DV-II+ Pro Viscometer with HelipathAccessory; chuck, weight and closer assembly for T-bar attachment; aT-bar Spindle D, a personal computer with Rheocalc software fromBrookfield, and a cable connecting the Brookfield Viscometer to thecomputer. First, weigh 40 grams of the cleansing phase in a 4-oz glassjar. Centrifuge the jar at 2,000 rpm for 20 min to de-aerate thecleansing phase, which may also remove large particles by sedimentationor flotation. Measure the height of the cleansing phase “H_(surf)” usingan Electronic Caliper with a precision of 0.01 mm. Measure the initialT-bar viscosity by carefully dropping the T-Bar Spindle to the interiorbottom of the jar and set the Helipath stand to travel in an upwarddirection. Open the Rheocalc software and set the following dataacquisition parameters: set Speed to 5 rpm, set Time Wait for Torque to00:01 (1 second), set Loop Start Count at 40. Start data acquisition andturn on the Helipath stand to travel upward at a speed of 22 mm/min. Theinitial T-Bar viscosity “T_(ini),” is the average T-Bar viscosityreading between the 6^(th) reading and the 35^(th) reading (the firstfive and the last five readings are not used for the average T-Barviscosity calculation). Cap the jar and store at ambient temperature.Prepare a separate lipid blend by heating a vessel to 180° F. (82.2° C.)and add together 70 parts of Petrolatum (G2218 from WITCO) and 30 partsof Hydrobrite 1000 White Mineral Oil. Cool the vessel to 110° F. (43.3°C.) with slow agitation (200 rpm). Stop agitation and cool the vessel toambient temperature overnight. Add 40 grams of the lipid blend (70/30Pet/MO) to the jar containing the first visually distinct phase. Stirthe first visually distinct phase and lipid together using a spatula for5 min. Place the jar at 113° F. (45° C.) for 5 days. After 5 days,centrifuge the jar at 2000 rpm for 20 min (do not cool the jar first).

After centrifugation, cool down the jar and contents to ambientconditions, overnight. Observe the contents of the jar. A stablecleansing phase exhibits a uniform layer at the bottom of the jar, belowthe less dense petrolatum/oil phase. An unstable cleansing phase canform layers not present in the originally centrifuged cleansing phase(i.e., an isotropic phase) either at the bottom or between the cleansingphase-lipid interface. If more than one layer is present in thecleansing phase, measure the height of each newly formed layer,“H_(new)” using an Electronic Caliper. Add together the heights of allthe newly formed layers. The new phase volume ratio is calculated asH_(new)/H_(surf)*100% , using the height of all new layers addedtogether as H_(new). Preferably, a stable structured cleansing phaseforms less than 10% of new phase volume. More preferably, a stablestructured cleansing phase forms less than 5% of new phase volume. Mostpreferably, a stable structured cleansing phase forms 0% of new phasevolume.

The T-Bar viscosity of the centrifuged contents of the jar is thenmeasured using the T-Bar method above. Open the Rheocalc software andset the following data acquisition parameters: set Speed to 5 rpm, setTime Wait for Torque to 00:01 (1 second), set Loop Start Count at 80.Start the data acquisition and turn on the Helipath stand to travelupward at a speed of 22 mm/min. There is usually a distinctive viscosityjump between the first visually distinct phase layer and the lipidlayer. The average cleansing phase T-Bar viscosity after lipid exposure,“T_(aft)” is the average reading between the 6^(th) T-Bar viscosity andthe last T-Bar viscosity reading before the jump in viscosity due to thelipid layer. In the case where there is no distinctive T-Bar viscosityjump between cleansing phase and lipid phase, only use the averagereading between the 6^(th) T-Bar viscosity reading and the 15^(th)reading as the average cleansing phase T-bar viscosity, T_(aft).Preferably, a stable structured cleansing phase has T_(aft) higher than10,000 cP. More preferably, a stable structured cleansing phase hasT_(aft) higher than 15,000 cP. Most preferably, a stable structuredfirst visually distinct phase has T_(aft) higher than 20,000 cPViscosity Retention is calculated as T_(aft)/T_(ini)*100%. Preferably, astable structured cleansing phase has >50% Viscosity Retention. Morepreferably, a stable structured cleansing phase has >70% ViscosityRetention. Most preferably, a stable structured cleansing phase has >80%Viscosity Retention.

Method of Use:

The multi-phase personal care compositions of the present invention arepreferably applied topically to the desired area of the skin or hair inan amount sufficient to provide effective delivery of the skin cleansingagent, hydrophobic material, and particles to the applied surface. Thecompositions can be applied directly to the skin or indirectly via theuse of a cleansing puff, washcloth, sponge or other implement. Thecompositions are preferably diluted with water prior to, during, orafter topical application, and then subsequently the skin or hair rinsedor wiped off, preferably rinsed off of the applied surface using wateror a water-insoluble substrate in combination with water.

The present invention is therefore also directed to methods of cleansingthe skin through the above-described application of the compositions ofthe present invention. The methods of the present invention are alsodirected to a method of providing effective delivery of the desired skinactive agent, and the resulting benefits from such effective delivery asdescribed herein, to the applied surface through the above-describedapplication of the compositions of the present invention.

Method of Manufacture:

The multi-phase personal care compositions of the present invention maybe prepared by any known or otherwise effective technique, suitable formaking and formulating the desired multi-phase product form. It iseffective to combine toothpaste-tube filling technology with a spinningstage design. Additionally, the present invention can be prepared by themethod and apparatus as disclosed in U.S. Pat. No. 6,213,166 issued toThibiant, et al on Apr. 10, 2001. The method and apparatus allows two ormore compositions to be filled with a spiral configuration into a singlecontainer. The method requires that at least two nozzles be employed tofill the container. The container is placed on a static mixer and spunas the composition is introduced into the container.

Alternatively, it is effective to combine at least two phases by firstplacing the separate compositions in separate storage tanks having apump and a hose attached. The phases are then pumped in predeterminedamounts into a single combining section. Next, the phases are moved fromthe combining sections into the blending sections and the phases aremixed in the blending section such that the single resulting productexhibits a distinct pattern of the phases. The pattern is selected fromthe group consisting of striped, marbled, geometric, and mixturesthereof. The next step involves pumping the product that was mixed inthe blending section via a hose into a single nozzle, then placing thenozzle into a container and filing the container with the resultingproduct. Specific non-limiting examples of such methods as they areapplied to specific embodiments of the present invention are describedin the following examples.

If the multi-phase personal care compositions are patterned, it can bedesirable to be packaged as a personal care article. The personal carearticle would comprise these compositions in a transparent ortranslucent package such that the consumer can view the pattern throughthe package. Because of the viscosity of the subject compositions it mayalso be desirable to include instructions to the consumer to store thepackage upside down, on its cap to facilitate dispensing.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationincludes every higher numerical limitation, as if such higher numericallimitations were expressly written herein. Every numerical range giventhroughout this specification includes every narrower numerical rangethat falls within such broader numerical range, as if such narrowernumerical ranges were all expressly written herein.

All parts, ratios, and percentages herein, in the Specification,Examples, and Claims, are by weight and all numerical limits are usedwith the normal degree of accuracy afforded by the art, unless otherwisespecified.

EXAMPLES

The following first visually distinct phases are prepared asnon-limiting examples (chemical content is shown). Examples 1 and 2 areComparative Examples of the first visually distinct phase of the presentinvention. Examples 3-7 are examples of the first visually distinctphase of the present invention. Examples 8, 9 and 10 are ComparativeExamples. Examples 11 and 12 are examples of structured aqueous phase ofthe present invention.

Examples 1 and 2 are comparative examples of the first visually distinctphase of the present invention which comprise all linear anionicsurfactants. Examples 3-5 are examples of the present inventioncomprising a mix of linear and branched anionic surfactants. Of themixed anionic surfactant compositions Examples 3-5, compositions withlower sodium trideceth sulfate exhibited higher flash and total lathervolumes. However, mixtures of branched and linear anionic surfactant(Examples 3-5) exhibited higher flash and total lather volume than alllinear anionic compositions (Comparative Examples 1 and 2), and improvedstability. First visually distinct Comparative Example phase example: 12 3 4 5 Water, distilled QS QS QS QS QS Skin Benefit Components andThickeners Water, distilled QS QS QS QS QS Glycerin 0.3 0.3 1.93 — —Guar hydroxypropropyl-trimonium chloride(N- 0.4 0.4 0.2 0.6 0.6 Hance3196 - Aqualon or Jaguar C-17, Rhodia) PEG 90M (Polyox WSR 301, AmercholCorp) 0.10 0.10 0.15 0.15 0.15 Citric acid — — 0.25 0.25 0.25 Structuredsurfactant components Sodium trideceth sulfate (Cedepal TD403, — — 6.177.9 7.9 Stepan) Ammonium Lauryl Sulfate (P&G) 13.4 9.40 9.26 7.9 7.9Sodium Lauroamphoacetate (Miranol L-32, — — 4.57 4.7 4.7 Rhodia)Polyoxyethylene 2.5 lauryl alcohol (Arylpon F, 3.0 2.1 — — — CognisCorp, Cincinnati, OH) Cocamidopropyl betaine (Tegobetaine F, 3.7 2.6 — —— DeGussa) Isosteareth-2 (Hetoxol IS-2, Global Seven, — — 1.0 1.0 1.0USA) Preservative and Minors Fragrance/perfume 1.4 1.4 1.54 1.54 1.44Sodium chloride 3.5 3.5 3.5 3.5 3.5 Disodium EDTA 0.06 0.06 0.12 0.120.12 DMDM Hydantoin (Glydant) 0.73 0.73 0.37 0.37 0.37 Sodium benzoate —— 0.2 0.2 0.2 Expancel 091 DE d30 microspheres (Akzo 0.3 0.3 0.3 0.3 0.3Nobel; Expancel, Inc.) Polymeric Phase Structurants Xanthan gum (KeltrolCGT, Kelco) 0.13 0.26 0.4 0.2 0.2 Acrylates/Vinyl IsodecanoateCrosspolymer 0.27 0.54 — — — (Stabylen 30 from 3V) Final pH (adjustusing NaOH or citric acid) 5.9 5.9 6.0 6.0 6.0 Total surfactant, % offirst visually distinct 20.1 14.1 21.0 21.5 21.5 phase Anionicsurfactant, % of structured surfactant 67 67 74 74 74 component Monomethyl branched anionic surfactant, % of 0 0 0 0 0 anionic surfactantBranched anionic surfactant, % of anionic 0 0 40 50 50 surfactant Zeroshear viscosity, Pa-sec 6800 7600 8100 4900 5700 Yield stress, Pa 14Lather Volume of first visually distinct phase: 490/1810 500/1930650/2340 540/2150 510/2020 Flash/Total (ml/ml) Structured Domain VolumeRatio 64 52 91 86 88 Stability: % Third Phase 0 6 0 0 0 T-bar %viscosity change −23 −37 −18 −15 −7

Examples 8-10 are Comparative Examples. Example 8 does not comprisebranched anionic surfactants. Comparative Examples 9 and 10 comprisehigher sodium trideceth sulfate than in the claimed range. Examples 6and 7, having lower sodium trideceth sulfate than Comparative Examples 9and 10, which have greater than 10% sodium trideceth sulfate, havehigher flash and total lather volumes. Comparative Example 8, which doesnot have any branched surfactants, is not stable, and also does not havelather volumes as high as Examples 6 and 7, which have both branched andlinear anionic surfactants. First visually distinct phase Example:Comparative Example 6 7 8 9 10 Water, distilled QS QS QS QS QS SkinBenefit Components and Thickeners Water, distilled QS QS QS QS QSGlycerin 0.21 0.3 0.5 0.5 Guar hydroxypropropyl-trimonium chloride(N-0.45 0.47 0.4 0.45 0.45 Hance 3196 - Aqualon or Jaguar C-17, Rhodia) PEG90M (Polyox WSR 301) 0.15 0.07 0.1 0.08 0.08 Citric acid 0.25 0.25 0.20.2 0.2 Structured surfactant components Sodium trideceth sulfate(Cedepal TD-403) 5.6 5.56 — 10.3 10.3 Safol 23 sulfate, sodium salt 5.56— — — Ammonium Lauryl Sulfate (P&G) 8.4 — — — — Ammonium Laureth Sulfate(P&G, 3 mol EO) — — 9.4 — — Cocamide monoethanolamine — — — 2.1 2.1Sodium Lauroamphoacetate (Miranol L-32) 3.0 — — 3.3 3.3 Polyoxyethylene2.5 lauryl alcohol (Arylpon F) 0.75 2.35 2.1 — — Cocamidopropyl betaine(Tegobetaine F) 3.35 2.58 — — Isosteareth-2 (Hetoxol IS-2) 1.0 1.0 — — —Preservative and Minors Fragrance/perfume 1.44 1.54 1.4 1.25 1.25 Sodiumchloride 3.5 3.5 3.5 2.8 2.8 Disodium EDTA 0.12 0.12 0.06 — — DMDMHydantoin (Glydant) 0.37 0.37 0.7 0.25 0.25 Sodium benzoate 0.2 0.2 — —— Expancel 091 DE d30 microspheres 0.3 0.3 0.3 — — Polymeric PhaseStructurants Xanthan gum (Keltrol CGT, Kelco) 0.4 0.66 0.26 — —Acrylates/Vinyl Isodecanoate Crosspolymer — — 0.54 0.5 0.8 (Stabylen 30from 3V) Final pH (adjust to) 6.0 6.2 5.9 6.7 5.8 Total surfactant, % ofsurfactant phase 18.8 17.8 14.1 15.7 15.7 Anionic surfactant, % ofstructured surfactant 75 62 67 56 56 component Mono methyl branchedanionic surfactant, % of 0 50 0 0 0 anionic surfactant Branched anionicsurfactant, % of anionic 40 100 0 100 100 surfactant Zero shearviscosity, Pa-sec 4600 4500 900 3300 8700 Lather Volume of firstvisually distinct phase: 590/2250 520/1910 470/1920 490/1840 460/1800Flash/Total (ml/ml) Structured Domain Volume Ratio 87 Stability: % ThirdPhase 0 0 5% 0 T-bar % viscosity change −20 −29 −79 −30

The first visually distinct phase can be prepared by conventional mixingtechniques. Prepare the first visually distinct phase by first addingthe water, skin benefit components and thickeners into a vessel,agitating until a dispersion is formed. Then add in the followingsequence: surfactants, Disodium EDTA, preservative, half the sodiumchloride and all other minors except fragrance and the withheld sodiumchloride. Heat to 65-70° C. if Cocamide monoethanolamine is used,otherwise maintain at ambient temperature while agitating the mixingvessel. Cool to 45 C if heating was used. For additional stability, gasfilled microspheres having a density of about 30 kg/m³ such as Expancel091 DE 40 d30 (from Expancel, Inc.) can optionally be used at about0.1-0.5% of the batch. In a separate vessel, prewet the structuringpolymers with fragrance and add to the mix vessel at the same time asthe remaining sodium chloride while agitating. Agitate untilhomogeneous, then pump through a static mixing element to disperse anylumps to complete the batch.

Structured Aqueous Phase

The Structured Aqueous Phase of Examples 11-12 can be prepared bydispersing polymers in water with high shear, adding salt and remainingingredients except petrolatum and mineral oil, neutralizing to pH 7.0with triethanolamine (approximate TEA level is shown), heating to 50°C., adding the petrolatum and mineral oil as a liquid at 80° C., andagitating until homogeneous without high shear. Pigments having no watersoluble components are preferably used. A particle size of about 5-100microns for the petrolatum component is obtained for most of theparticles. Structured Aqueous Phase (non-lathering) Example: 11 12Water, distilled QS QS Acrylates/Vinyl Isodecanoate Crosspolymer 1.0 0.8(Stabylen 30 from 3V) Xanthan gum (Keltrol CGT or Keltrol 1000 1.0 0.8from Kelco) DMDM Hydantoin, preservative 0.4 0.4 EDTA 0.05 0.04 Mineraloil (Hydrobrite 1000, Witco) 0.03 4.82 Petrolatum (Super White Protopet,Witco) 20.0 18.78 Triethanolamine 0.80 0.80 Sodium chloride 3.0 2.4Pigment 0.35 0.35Visually Distinct Compositions

Visually distinct compositions are prepared by first preparing twocompositions that differ in appearance. A first visually distinct phasesof Examples 3-7 is selected (any can be selected) and pigmented using ahydrophobic pigment, which keeps color from leaching. A second firstvisually distinct phase of Examples 3-7 and 11-12 can be selected andeither pigmented to a different color, pigmented white, or notpigmented, such that the phase visually differs from the first phasechosen, including by being, e.g., a transparent gel. The phases areadded to separate hoppers and gravity fed to a package (e.g., bottle,tube, etc.) filling operation. The phases are maintained at ambienttemperature and are simultaneously pumped in a specified volumetricratio through ¾ in. diameter pipes containing a single element staticmixer (Koch/SMX type), the single pipe exits into a 10 oz. bottle on aspinning platform. The platform is set to 200 rpm spin speed, thecomposition filling 315 ml in about 2 seconds, the spinning platformbeing lowered during filling so that filling proceeds in a layeringfashion from bottom to top. A relatively horizontal striped pattern isobtained. By adjusting temperature and viscosity of the phases, staticmixer element types and number of elements (including no elements), pipediameters, spin rates, etc., a wide variety of patterns is obtained. Oneor both of the phases can be a benefit phase, or a combined benefitphase, by preparing an emulsion or a dispersion with the phase usingconventional techniques to prepare an emulsion or dispersion with adispersed phase such as petrolatum, mineral oil, other synthetic andnatural oils such as jojoba, shea butter, triglyceride, lanolin, ethers,esters including emollient sucrose esters, ethers, waxes, siliconefluids, polymers including polymeric esters such as polyglyceryl esters,mixtures and combinations of these and other hydrophobic materialshaving a Vaughn Solubility Parameter less than about 13 (cal/cm³)^(1/2).When mixtures of such hydrophobic materials are used, they can beprepared by combining the hydrophobic materials first at an elevatedtemperature, such as is done in traditional emulsion preparation, orthey can be added separately, either with heat or without, in a batch,semi-batch, or continuous process to the hydrophilic phase. Colorant,pigment or whitener can be added to the dispersed phase or to either ofthe hydrophilic continuous phases. To optimize benefit phase efficacyand/or appearance, any of the Examples 3-7 can be diluted to a lowersurfactant concentration, e.g. to 10%, or 6%, or 4% or even less than 1%surfactant so long as the phase remains continuously hydrophilic and therheology of the phase sufficient so the visually distinct compositionremains stable. The hydrophobic material can also be dispersed in anon-lathering structured aqueous phase, for example the non-latheringstructured aqueous phase of Examples 1 or 12, as shown. The benefitphase can thus be lathering, or non-lathering. If the surfactant levelis reduced in one of the phases, rheology can be adjusted usingtraditional thickeners, for example water soluble polymers, cross-linkedwater swellable polymers, clays, gel networks, etc., as is known to onewith ordinary skill in the art. Additionally, surfactant can beconcentrated in one of the phases by reducing water content, so that thesurfactant concentration is 24%, 30%, 40%, 50% or even as high as 75% ofone or more of the phases in order to deliver efficient cleansing from alow level of a concentrated surfactant phase. Typically, levels ofelectrolyte (e.g., salt), thickeners and cationic polymer would beadjusted for viscosity control. In some cases, it may be preferred toincrease viscosity, for example so that the Zero Shear Viscosity isgreater than 15,000 Pa-sec, even greater than 25,000 Pa-sec, or evengreater than 35,000 Pa-sec in order to provide phases which are visuallydistinct and paste-like, such as for example visually distinctconcentrates packaged in tubes, filled by apparati such as multi-phasetoothpaste filling equipment.

Additionally, the present invention can be prepared by the method andapparatus as disclosed in U.S. Pat. No. 6,213,166 issued to Thibiant et,al. on Apr. 10, 2001 which method and apparatus allows compositions tobe filled with a spiral configuration into a single container using atleast 2 nozzles.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this written document conflicts with any meaningor definition of the term in a document incorporated by reference, themeaning or definition assigned to the term in this written documentshall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

1. A multi-phase personal care composition comprising: a first visuallydistinct phase comprising a structured surfactant component; and asecond visually distinct phase; wherein said structured surfactantcomponent comprises at least one branched anionic surfactant and from 0to 10%, by weight of said first visually distinct phase, of sodiumtrideceth sulfate.
 2. The multi-phase personal care composition of claim1, wherein said structured surfactant component comprises 0.1% to 10%,by weight of said first visually distinct phase, of sodium tridecethsulfate.
 3. The multi-phase personal care composition of claim 1,wherein said structured surfactant component comprises 9.5%, by weightof said first visually distinct phase, of sodium trideceth sulfate. 4.The multi-phase personal care composition of claim 1, wherein saidcomposition comprises from about 2% to about 23.5%, by weight of saidfirst visually distinct phase, of said structured surfactant component.5. The multi-phase personal care composition of claim 1, wherein saidcomposition comprises from about 3% to about 21%, by weight of saidfirst visually distinct phase, of said structured surfactant component.6. The multi-phase personal care composition of claim 1, wherein saidbranched anionic surfactant is selected from the group consisting ofsodium trideceth sulfate, sodium tridecyl sulfate, ammonium tridecethsulfate, ammonium tridecyl sulfate, monomethyl branched sulfatedderivatives of branched hydrocarbons, and mixtures thereof.
 7. Themulti-phase personal care composition of claim 6, wherein said branchedanionic surfactant comprises monomethyl branched sulfated derivatives ofhydrocarbons.
 8. The multi-phase personal care composition of claim 1,wherein said first visually distinct phase provides a Yield Stress ofgreater than about 1.5 Pascal.
 9. The multi-phase personal carecomposition of claim 1, wherein said composition further comprises apolymeric phase structurant.
 10. The multi-phase personal carecomposition of claim 9, wherein said polymeric phase structurant isselected from the group consisting of deflocculating polymers, naturallyderived polymers, synthetic polymers, crosslinked polymers, blockpolymers, block copolymers, copolymers, hydrophilic polymers, nonionicpolymers, anionic polymers, hydrophobic polymers, hydrophobicallymodified polymers, associative polymers, oligomers, and mixturesthereof.
 11. The multi-phase personal care composition of claim 9,wherein said multi-phase personal care composition comprises from about0.05% to about 10%, by weight of said first visually distinct phase, ofsaid polymeric phase structurant.
 12. The multi-phase personal carecomposition of claim 1, wherein said first visually distinct phase andsaid second visually distinct phase form a pattern.
 13. The multi-phasepersonal care composition of claim 12 wherein the pattern is selectedfrom the group consisting of striped, geometric, marbled, andcombinations thereof.
 14. The multi-phase personal care composition ofclaim 12, wherein said composition is packaged in a container such thatsaid pattern is visible.
 15. The multi-phase personal care compositionof claim 1, wherein said first visually distinct phase furthercomprises: (i) at least one electrolyte; (ii) at least one alkanolamide;and (iii) water; wherein said first visually distinct phase isnon-Newtonian shear thinning; and wherein
 16. The multi-phase personalcare composition of claim 1, wherein said first visually distinct phasecomprises: (a) said structured surfactant component further comprising:(i) at least one nonionic surfactant having an HLB from about 3.4 toabout 15.0; (ii) at least one amphoteric surfactant; and (b) anelectrolyte.
 17. The multi-phase personal care composition of claim 1,wherein said first visually distinct phase further comprises a liquidcrystalline phase inducing structurant.
 18. The multi-phase personalcare composition of claim 17, wherein said liquid crystalline phaseinducing structurant is selected from the group consisting of fattyacids, fatty alcohols, fatty esters, trihydroxystrearin, and mixturesthereof.
 19. The structured, multi-phase personal cleansing compositionof claim 1, wherein said composition additionally comprises a benefitcomponent, wherein said benefit component is selected from the groupconsisting of emollients, particles, beads, skin whitening agents,fragrances, colorants, vitamins and derivatives thereof, sunscreens,preservatives, anti-acne medicaments, antioxidants, chelators, essentialoils, skin sensates, antimicrobial, and mixtures thereof.